EP0066224A1 - Preparation of a glutaraldehyde precursor - Google Patents

Preparation of a glutaraldehyde precursor Download PDF

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Publication number
EP0066224A1
EP0066224A1 EP82104482A EP82104482A EP0066224A1 EP 0066224 A1 EP0066224 A1 EP 0066224A1 EP 82104482 A EP82104482 A EP 82104482A EP 82104482 A EP82104482 A EP 82104482A EP 0066224 A1 EP0066224 A1 EP 0066224A1
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Prior art keywords
glutaraldehyde
dihydropyran
water
reaction
acid
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EP0066224B1 (en
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Nan Shieh Chu
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Union Carbide Corp
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/10—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings

Definitions

  • This invention is directed to a process for the preparation of a novel essentially nonaqueous glutaraldehyde precursor which is capable of rapidly generating glutaraldehyde upon addition to water.
  • the precursor is prepared by the hydration of 2-alkoxy-3,4-dihydropyran in the presence of an acid catalyst.
  • Glutaraldehyde is widely used in many applications, such as leather tanning, embalming, photography and particularly as a microbiocide.
  • Glutaraldehyde is generally prepared by the acid hydrolysis of 2-alkoxy-3,4-dihydropyran in a system containing a large excess of water, Without water, glutaraldehyde is generally not stable and polymerizes to a glassy-mass on standing. Thus, it is always prepared as an aqueous solution.
  • a commercial concentration generally contains from about 50 to about 98 percent water. However, even this aqueous glutaraldehyde solution is capable of polymerizing to an oligomer and/or to a polymer which precipitates from the aqueous solution on standing.
  • glutaraldehyde undergoes an alool condensation.
  • the formation of these condensation products, as well as oligomers and/or polymers increases with, for example, increasing temperature, glutaraldehyde concentration, and pH.
  • the current processes for preparing glutaraldehyde have drawbacks.
  • the formation of the condensation products and/or oligomers and polymers results in the loss of glutaraldehyde.
  • the use of 50 percent or more of water during the acid hydrolysis of the 2-alkoxy-3,4-dihydropyran decreases reactor capacity.
  • thermal stability of the solution becomes a serious problem.
  • the aqueous solution may freeze.
  • U.S. Patent 4,244,876 describes the formation of a precursor to glutaraldehyde, i,e., 2,6 dimethoxytetra hydropyran. It is prepared by the addition of an alcohol to 2-methoxy-3,4-dihydropyran.
  • glutaraldehyde is produced from the 2,6 dimethoxytetrahydropyran.
  • the conditions under which the glutaraldehyde is produced from the 2,6 dimethoxytetrahydropyran are time consuming, since it requires several hours at low pH to generate a substantial amount of glutaraldehyde.
  • U.S. Patent 2,546,018 describes the preparation of glutaraldehyde by heating a derivative of dihydropyran, for example, a 2-alkoxy-3,4-dihydropyran with water.
  • the principal product of the reaction is glutaraldehyde.
  • This invention is directed to a process for the preparation of a novel essentially nonaqueous glutaraldehyde precursor.
  • the precursor is prepared by hydrating 2-alkoxy-3,4-dihydropyran in the presence of an acid catalyst at a temperature of from about 30 to about 100°C and wherein the molar ratio of water to 2-alkoxy-3,4-dihydropyran is from about 1:1 to about 3:1.
  • the hydration conditions are such that materials containing appreciable and substantial carbonyl content are not produced, i.e., essentially no free glutaraldehyde is produced.
  • the hydration product produced does not polymerize, Also, it has better thermal stability and a lower freezing point than a commercial 50 percent or greater glutaraldehyde solution.
  • the hydration product yields glutaraldehyde upon addition to water.
  • reaction may be illustrated by the hydration of, for example, 2-methoxy-3,4-dihydropyran:
  • the principal product is 2-hydroxyl-6-methoxytetrahydropyran (I) although trace amounts of 2,6-dimethoxytetrahydropyran (II) glutaraldehyde (III) and their isomers are formed.
  • the reaction is carried out in the presence of an acid catalyst.
  • the acid catalyst may be an inorganic or an organic acid or an ion exchange resin.
  • the acids which may be used herein include a strong mineral acid, an acid-reacting salt, a material which will react under the conditions of the process to form in situ, an acid-reacting material or a supported acid catalyst.
  • These acid catalysts include phosphoric acid, hydrochloric acid, sulfuric acid, trifluoromethyl- sulfonic acid, para-toluenesulfonic acid, as well as supported acid catalysts, such as Amberlyst which is a supported arylsulfonic acid (sold by Rohm & Haas Company) and Nafion which is a supported fluorosulfonic acid (sold by E. I. duPont de Nemours Co.).
  • Amberlyst which is a supported arylsulfonic acid (sold by Rohm & Haas Company)
  • Nafion which is a supported fluorosulfonic acid (sold by E. I. duPont de Nemours Co.).
  • the acid may be removed after hydration by neutralizing it with a base to form a salt and then removing the salt, as by filtration.
  • the reaction is carried out at a temperature of from about 30 to about 100°C, and preferably from about 40 to about 90°C.
  • the reaction temperature and time are dependent upon the type and amount of catalyst used in the reaction.
  • the reaction is generally carried out at atmospheric pressure, although subatmospheric and superatmospheric pressures may be used.
  • the molar ratio of water to 2-alkoxy-3,4-dihydropyran in the reaction is from about 1:1 to about 3:1, and preferably from about 1:1 to about 2:1.
  • the use of larger amounts of water offer no advantages since reactor capacity is reduced and the shelf-life of the reaction product is reduced.
  • the alkoxy group of the 2-alkoxy-3,4-dihydropyran preferably contains from 1 to 3 carbon atoms.
  • the reaction product may be used as such. It is added to water to produce glutaraldehyde.
  • the water may contain optional ingredients such as colorants, thickeners, fragrances, and the like. However, water is the predominant material.
  • reaction vessel A 250 ml 4-necked round bottom flask, fitted with a condenser, a mechanical stirrer, a thermometer and a nitrogen inlet was used as the reaction vessel.
  • the flask was flushed with nitrogen and 114 g. of 2-methoxy-3,4-dihydropyran, 21.6 g. of distilled water and 13.2 of Rexyn 101, a sulfonated polystyrene (supplied by Fisher Scientific Co.) were added.
  • the catalyst resin was rewashed with distilled water to remove most.of the water soluble acids which might be present.
  • the resin contained 5 milliequivalents of acid per gram of dry resin.
  • the reaction mixture was kept in a constant temperature bath of 50°C.
  • Example 1 The procedure described in Example 1 was exactly repeated except that the molar ratio of water to 2-methoxy-3,4-dihydropyran was varied in Examples 2 to 4 as follows: 1.0/1.2; 1.0/2.0 and 1.0/5.6. After the reaction was complete, portions of the reaction products were stored in an oven set at a temperature of 60°C for 27 days of thermal aging. 25 percent solutions of the aged samples in water were prepared and their UV absorbance (at 233 nm) were measured in a 0.1 mm silica cell (vs. air). (Beckman ACTA Model M VIII). The absorbences of the reaction product before and after thermal aging are listed in Table I. The 233 nm absorbence indicates the formation of undesirable aldol type condensation products.
  • Control A is a 50 percent glutaraldehyde solution.
  • Example 1 The procedure described in Example 1 was exactly repeated except that the amounts of materials used were as follows: 28.5g of 2-methoxy-3,4-dihydropyran, 5.4g of distilled water and 6.6g of catalyst. Also, the reaction was carried out at a temperature of 35°C instead of 50°C. The reaction was complete in about 2 hours.
  • Example 1 The procedure in Example 1 was exactly repeated except that the amounts of materials used were as follows: 28.5 g of 2-methoxy-3,4-dihydropyran and 4.5 g of distilled water. Also 1.0 g of Nafion-511,H (0.95 milliequivalents per gram, supplied by E. I. DuPont de Nemours & Co.) was used instead of the Rexyn 10 catalyst. The reaction was complete in about 40 minutes.
  • Example 1 The procedure in Example 1 was exactly repeated except that the amounts of materials used were as follows: 28.5g of 2-methoxy-3,4-dihydropyran and 5.4g of distilled water. Also, 0.5g of an 85 percent phosphoric acid solution was used at the catalyst instead of Rexyn 101. The reaction was carried out at a temperature of 90°C instead of 50°C. The reaction was complete in about 90 minutes. The reaction product was cooled to room temperature (about 25°C) and adjusted to a pH of 7 with 0.36 g of sodium bicarbonate. The reaction product was filtered to remove a small amount of precipitate.
  • Example 17 The procedure of Example 17 was exactly repeated except that 1.0 g of the phosphoric acid solution was used. Also, the reaction was carried out at a temperature of 65°C. The reaction was complete in about 2 to 2 1/2 hours. The reaction product was cooled to room temperature (about 25°C) and adjusted to a pH of 7 with 0.72 g of sodium bicarbonate. The reaction product was filtered to remove a small amount of precipitate.

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Abstract

Described herein is a process for the preparation of a novel essentially nonaqueous glutaraldehyde precursor which is capable of rapidly generating glutaraldehyde upon addition to water. The precursor is prepared by the hydration of 2-alkoxy-3,4-dihydropyran in the presence of an acid catalyst.

Description

  • This invention is directed to a process for the preparation of a novel essentially nonaqueous glutaraldehyde precursor which is capable of rapidly generating glutaraldehyde upon addition to water. The precursor is prepared by the hydration of 2-alkoxy-3,4-dihydropyran in the presence of an acid catalyst.
  • Glutaraldehyde is widely used in many applications, such as leather tanning, embalming, photography and particularly as a microbiocide. Glutaraldehyde is generally prepared by the acid hydrolysis of 2-alkoxy-3,4-dihydropyran in a system containing a large excess of water, Without water, glutaraldehyde is generally not stable and polymerizes to a glassy-mass on standing. Thus, it is always prepared as an aqueous solution. A commercial concentration generally contains from about 50 to about 98 percent water. However, even this aqueous glutaraldehyde solution is capable of polymerizing to an oligomer and/or to a polymer which precipitates from the aqueous solution on standing.
  • Further, glutaraldehyde undergoes an alool condensation. The formation of these condensation products, as well as oligomers and/or polymers increases with, for example, increasing temperature, glutaraldehyde concentration, and pH.
  • The current processes for preparing glutaraldehyde have drawbacks. The formation of the condensation products and/or oligomers and polymers results in the loss of glutaraldehyde. Also, the use of 50 percent or more of water during the acid hydrolysis of the 2-alkoxy-3,4-dihydropyran decreases reactor capacity. Further, when the commercial 50 percent aqueous solution is shipped to warm climates, thermal stability of the solution becomes a serious problem. Also, in cold weather the aqueous solution may freeze.
  • Thus, there is much interest in developing a nonaqueous precursor to glutaraldehyde capable of yielding glutaraldehyde upon its addition to water. Such a precursor could be stored or shipped in varying climates without the resulting problems now associated with an aqueous solution.
  • U.S. Patent 4,244,876 describes the formation of a precursor to glutaraldehyde, i,e., 2,6 dimethoxytetra hydropyran. It is prepared by the addition of an alcohol to 2-methoxy-3,4-dihydropyran. However, the conditions under which the glutaraldehyde is produced from the 2,6 dimethoxytetrahydropyran are time consuming, since it requires several hours at low pH to generate a substantial amount of glutaraldehyde.
  • U.S. Patent 2,546,018 describes the preparation of glutaraldehyde by heating a derivative of dihydropyran, for example, a 2-alkoxy-3,4-dihydropyran with water. The principal product of the reaction is glutaraldehyde. Thus, the problems associated with aqueous or nonaqueous glutaraldehyde still exists.
  • In the present invention a novel essentially nonaqueous glutaraldehyde has been discovered.
    • ,THE INVENTION
  • This invention is directed to a process for the preparation of a novel essentially nonaqueous glutaraldehyde precursor. The precursor is prepared by hydrating 2-alkoxy-3,4-dihydropyran in the presence of an acid catalyst at a temperature of from about 30 to about 100°C and wherein the molar ratio of water to 2-alkoxy-3,4-dihydropyran is from about 1:1 to about 3:1. The hydration conditions are such that materials containing appreciable and substantial carbonyl content are not produced, i.e., essentially no free glutaraldehyde is produced.
  • The hydration product produced does not polymerize, Also, it has better thermal stability and a lower freezing point than a commercial 50 percent or greater glutaraldehyde solution. The hydration product yields glutaraldehyde upon addition to water.
  • The reaction may be illustrated by the hydration of, for example, 2-methoxy-3,4-dihydropyran:
    Figure imgb0001
  • The principal product is 2-hydroxyl-6-methoxytetrahydropyran (I) although trace amounts of 2,6-dimethoxytetrahydropyran (II) glutaraldehyde (III) and their isomers are formed.
  • The reaction is carried out in the presence of an acid catalyst. The acid catalyst may be an inorganic or an organic acid or an ion exchange resin. The acids which may be used herein include a strong mineral acid, an acid-reacting salt, a material which will react under the conditions of the process to form in situ, an acid-reacting material or a supported acid catalyst. These acid catalysts include phosphoric acid, hydrochloric acid, sulfuric acid, trifluoromethyl- sulfonic acid, para-toluenesulfonic acid, as well as supported acid catalysts, such as Amberlyst which is a supported arylsulfonic acid (sold by Rohm & Haas Company) and Nafion which is a supported fluorosulfonic acid (sold by E. I. duPont de Nemours Co.). When a liquid acid is used, the acid may be removed after hydration by neutralizing it with a base to form a salt and then removing the salt, as by filtration.
  • The reaction is carried out at a temperature of from about 30 to about 100°C, and preferably from about 40 to about 90°C. The reaction temperature and time are dependent upon the type and amount of catalyst used in the reaction.
  • The reaction is generally carried out at atmospheric pressure, although subatmospheric and superatmospheric pressures may be used.
  • The molar ratio of water to 2-alkoxy-3,4-dihydropyran in the reaction is from about 1:1 to about 3:1, and preferably from about 1:1 to about 2:1. The use of larger amounts of water offer no advantages since reactor capacity is reduced and the shelf-life of the reaction product is reduced.
  • The alkoxy group of the 2-alkoxy-3,4-dihydropyran preferably contains from 1 to 3 carbon atoms.
  • The reaction product may be used as such. It is added to water to produce glutaraldehyde. The water may contain optional ingredients such as colorants, thickeners, fragrances, and the like. However, water is the predominant material.
    • EXAMPLES
  • The following examples serve to give specific illustrations of the practice of this invention but they are not intended in any way to limit the scope of this invention.
    • Example 1
  • A 250 ml 4-necked round bottom flask, fitted with a condenser, a mechanical stirrer, a thermometer and a nitrogen inlet was used as the reaction vessel. The flask was flushed with nitrogen and 114 g. of 2-methoxy-3,4-dihydropyran, 21.6 g. of distilled water and 13.2 of Rexyn 101, a sulfonated polystyrene (supplied by Fisher Scientific Co.) were added. The catalyst resin was rewashed with distilled water to remove most.of the water soluble acids which might be present. The resin contained 5 milliequivalents of acid per gram of dry resin. The reaction mixture was kept in a constant temperature bath of 50°C. The hydration was followed gas chromatographically (Hewlett-Packard Model 571(A) to completion by the disappearance of the 2-methoxy-3,4-dihydropyran peak. The reaction was carried out for about 2 to 2 1/2 hours. The reaction was cooled to room temperature (about 25°C) and the reaction product filtered. A slightly yellow liquid was obtained. The yield was about 98 percent.
    • EXAMPLES 2 TO 4
  • The procedure described in Example 1 was exactly repeated except that the molar ratio of water to 2-methoxy-3,4-dihydropyran was varied in Examples 2 to 4 as follows: 1.0/1.2; 1.0/2.0 and 1.0/5.6. After the reaction was complete, portions of the reaction products were stored in an oven set at a temperature of 60°C for 27 days of thermal aging. 25 percent solutions of the aged samples in water were prepared and their UV absorbance (at 233 nm) were measured in a 0.1 mm silica cell (vs. air). (Beckman ACTA Model M VIII). The absorbences of the reaction product before and after thermal aging are listed in Table I. The 233 nm absorbence indicates the formation of undesirable aldol type condensation products.
    Figure imgb0002
  • The data in-Table I show that as the ratio of water to 2-methoxy-3,4-dihydropyran increases the solutions are less thermally stable.
    • Examples 5 to 7
  • These Examples demonstrate the rapid generation of glutaraldehyde when the reaction products produced by the hydration of 2-methoxy-3,4-dihydropyran are added to water at room temperature (about 25°C). The reaction products were prepared as described in Example 1 with the mole ratio of water to 2-methoxy-3,4-dihydropyran in Examples 5 to 7 as follows: 1.0/1.0; 1.5/1.0 and 2.0/1.0. within five minutes after addition to water, gas chromatograph analyses was used to show the generation of the glutaraldehyde. These aqueous solutions were prepared to contain equivalent amounts of 2-methoxy-3,4-dihydropyran.
    Figure imgb0003
    • Examples 8 to 10
  • These Examples demonstrate the heat stability of the reaction product produced by the hydration of 2-methoxy-3,4-dihydropyran prepared as in'Example 1. The mole ratio of water to 2-methoxy-3,4-dihydropyran in Examples 8 to 10 was as follows: 1.2/1.0; 1.5/1.0 and 2.0/1.0. The reaction products were thermally aged for the time periods and at the temperatures shown in Table III. After thermally aging, the reaction Products were added to water to reflect an equivalent initial pyran'concentration. Gas chromatograph analysis was used to show the concentration of glutaraldehyde. The untreated sample was also analyzed.
  • Control A is a 50 percent glutaraldehyde solution.
  • The results are shown in Table III.
    Figure imgb0004
  • The data in Table III show that the reaction product of this invention is more thermally stable than. the 50 percent.aqueous glutaraldehyde solution.
    • Examples 11 to 14
  • These Examples demonstrate that the rapid generation of glutaraldehyde from the 2-hydroxy-6-methoxytetrahydropyran reaction product make this product a very effective microbiocide. The products were prepared by the procedure described in Example 1. The mole ratio of water to 2-methoxy-3,4-dihydropyran in Examples 11 to 14 was as follows: 1.0/1.0; 1.2/1.0; 1.5/1.0 and 2.0/1.0. The concentration of reaction products required to kill all the staphylococcus aureus (107 colony forming units/milliliter) present with 2 hours contact time using a solution having a pH of 7 are shown in Table IV.
    Figure imgb0005
    • Example 15
  • The procedure described in Example 1 was exactly repeated except that the amounts of materials used were as follows: 28.5g of 2-methoxy-3,4-dihydropyran, 5.4g of distilled water and 6.6g of catalyst. Also, the reaction was carried out at a temperature of 35°C instead of 50°C. The reaction was complete in about 2 hours.
    • Example 16
  • The procedure in Example 1 was exactly repeated except that the amounts of materials used were as follows: 28.5 g of 2-methoxy-3,4-dihydropyran and 4.5 g of distilled water. Also 1.0 g of Nafion-511,H (0.95 milliequivalents per gram, supplied by E. I. DuPont de Nemours & Co.) was used instead of the Rexyn 10 catalyst. The reaction was complete in about 40 minutes.
    • Example 17
  • The procedure in Example 1 was exactly repeated except that the amounts of materials used were as follows: 28.5g of 2-methoxy-3,4-dihydropyran and 5.4g of distilled water. Also, 0.5g of an 85 percent phosphoric acid solution was used at the catalyst instead of Rexyn 101. The reaction was carried out at a temperature of 90°C instead of 50°C. The reaction was complete in about 90 minutes. The reaction product was cooled to room temperature (about 25°C) and adjusted to a pH of 7 with 0.36 g of sodium bicarbonate. The reaction product was filtered to remove a small amount of precipitate.
    • Example 18
  • The procedure of Example 17 was exactly repeated except that 1.0 g of the phosphoric acid solution was used. Also, the reaction was carried out at a temperature of 65°C. The reaction was complete in about 2 to 2 1/2 hours. The reaction product was cooled to room temperature (about 25°C) and adjusted to a pH of 7 with 0.72 g of sodium bicarbonate. The reaction product was filtered to remove a small amount of precipitate.

Claims (7)

1. A process for'producing a glutaraldehyde precursor which comprises hydrating 2-alkoxy-3,4-dihydropyran in the presence of an acid catalyst at a temperature of from about 30 to about 100°C, wherein the ratio of water to 2-alkoxy-3,4-dihydropyran is from about 1:1 to about 3:1 and wherein the alkoxy group contains from 1 to 3 carbon atoms.
2. A process as defined in claim 1 wherein the 2-alkoxy-3,4-dihydropyran is 2-methoxy-3,4-dihydropyran.
3. An essentially nonaqueous product comprising 2-hydroxy-6-methoxytetrahydropyran, 2,6-dimethoxyteira- hydropyran, glutaraldehyde, and isomers thereof.
4. An essentially nonaqueous product comprising 2-hydroxy-6-methoxytetrahydropyran and 2,6-dimethoxytetrahydropyran..
5. 2-hydroxy-6-methoxytetrahydropyran.
6. A process for producing an aqueous solution of glutaraldehyde which comprises adding the reaction product of claim 1 to water.
7. A process for producing an aqueous solution of glutaraldehyde which comprises adding 2-hydroxy-6-methoxytetrahydropyran tc water.
EP82104482A 1981-05-21 1982-05-21 Preparation of a glutaraldehyde precursor Expired EP0066224B1 (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
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JPS59108734A (en) * 1982-12-13 1984-06-23 Daicel Chem Ind Ltd Preparation of glutaraldehyde
EP0697392A1 (en) 1994-08-18 1996-02-21 Basf Aktiengesellschaft Process for the preparation of glutaraldehyde
EP0717026A1 (en) 1994-12-15 1996-06-19 Basf Aktiengesellschaft Process for the preparation of glutaraldehyde
WO1996025040A1 (en) * 1995-02-16 1996-08-22 Degussa Aktiengesellschaft Composition capable of releasing acraldehyde and its use
US5696052A (en) * 1994-11-21 1997-12-09 Degussa Aktiengesellschaft Method and composition for combatting microbial, vegetable and animal pests with acrolein
US6559346B1 (en) 1999-08-30 2003-05-06 Basf Aktiengesellschaft Method for the continuous production of glutaraldehyde
WO2004067782A1 (en) * 2003-01-28 2004-08-12 Basf Aktiengesellschaft Tanning agents and preservatives
US7410504B2 (en) 2003-01-28 2008-08-12 Basf Aktiengesellschaft Adducts based on cyclic compounds and the use thereof as tanning agents and curing agents
CN100425342C (en) * 2005-04-21 2008-10-15 上海华谊丙烯酸有限公司 Zeolite catalyst and its use for hydrolysis reaction of dihydropyran derivatives
WO2018073010A1 (en) 2016-10-18 2018-04-26 Basf Se Processes for making leather

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US2694077A (en) * 1952-02-19 1954-11-09 Union Carbide & Carbon Corp Production of hydroxy derivatives of methacrolein dimer
FR1255546A (en) * 1960-02-16 1961-03-10 Du Pont Preparation of alpha-epsilon-diaminopimelic acid from trimethylene-bis- (5, 5 ') hydantoin and process for the preparation of the latter
US4244876A (en) * 1978-11-17 1981-01-13 Union Carbide Corporation Acetal-acid compositions

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US2546018A (en) * 1947-09-06 1951-03-20 Shell Dev Production of glutaraldehyde and csubstituted glutaraldehyde from dihydro pyrans
US2694077A (en) * 1952-02-19 1954-11-09 Union Carbide & Carbon Corp Production of hydroxy derivatives of methacrolein dimer
FR1255546A (en) * 1960-02-16 1961-03-10 Du Pont Preparation of alpha-epsilon-diaminopimelic acid from trimethylene-bis- (5, 5 ') hydantoin and process for the preparation of the latter
US4244876A (en) * 1978-11-17 1981-01-13 Union Carbide Corporation Acetal-acid compositions

Cited By (14)

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JPS59108734A (en) * 1982-12-13 1984-06-23 Daicel Chem Ind Ltd Preparation of glutaraldehyde
EP0697392A1 (en) 1994-08-18 1996-02-21 Basf Aktiengesellschaft Process for the preparation of glutaraldehyde
US5600018A (en) * 1994-08-18 1997-02-04 Basf Aktiengesellschaft Preparation of glutaraldehyde
US5696052A (en) * 1994-11-21 1997-12-09 Degussa Aktiengesellschaft Method and composition for combatting microbial, vegetable and animal pests with acrolein
CN1064665C (en) * 1994-12-15 2001-04-18 Basf公司 Preparation of glutaric dialdehyde
EP0717026A1 (en) 1994-12-15 1996-06-19 Basf Aktiengesellschaft Process for the preparation of glutaraldehyde
US5679868A (en) * 1994-12-15 1997-10-21 Basf Aktiengesellschaft Preparation of glutaric dialdehyde
WO1996025040A1 (en) * 1995-02-16 1996-08-22 Degussa Aktiengesellschaft Composition capable of releasing acraldehyde and its use
US6559346B1 (en) 1999-08-30 2003-05-06 Basf Aktiengesellschaft Method for the continuous production of glutaraldehyde
WO2004067782A1 (en) * 2003-01-28 2004-08-12 Basf Aktiengesellschaft Tanning agents and preservatives
US7282066B2 (en) 2003-01-28 2007-10-16 Basf Aktiengesellschaft Processes for preparing and using tanning agents and preservatives
US7410504B2 (en) 2003-01-28 2008-08-12 Basf Aktiengesellschaft Adducts based on cyclic compounds and the use thereof as tanning agents and curing agents
CN100425342C (en) * 2005-04-21 2008-10-15 上海华谊丙烯酸有限公司 Zeolite catalyst and its use for hydrolysis reaction of dihydropyran derivatives
WO2018073010A1 (en) 2016-10-18 2018-04-26 Basf Se Processes for making leather

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Publication number Publication date
EP0066224B1 (en) 1985-03-20
JPS57203081A (en) 1982-12-13
NO821570L (en) 1982-11-22
DE3262622D1 (en) 1985-04-25
NO159381B (en) 1988-09-12
NO159381C (en) 1988-12-21
MX160634A (en) 1990-03-29
JPS6052151B2 (en) 1985-11-18
CA1175850A (en) 1984-10-09
ATE12221T1 (en) 1985-04-15

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